STUDIES ON ACID VALUE REDUCTION OF

RUBBER SEED OIL AND BIODIESEL PRODUCTION

Eldhose K Joy, Jilse Sebastian, Chandrasekharan Muraleedharan
National Institute of Technology Calicut, NIT Campus (P.O), Kozhikode, Kerala.
PIN-673601, INDIA

Abstract
Biodiesels produced from a wide variety of vegetable oils are expected to replace diesel
fuel. Conventional biodiesel production method from edible or non-edible type oils is
alkaline transesterification. The conflict between food and fuel led for identifying more
than fifty non-edible oil sources that can be used for biodiesel production. Rubber seed oil,
easily available one among them, is applied to two step acid esterification process to
reduce the high free fatty acid (FFA) content from 41% to 2.03% with 80% methanol and
2% acid catalyst in 2 hour reaction time. Acid esterification was carried out by 50% (v/v)
methanol with 1% (v/v) sulphuric acid (H2SO4) as the acid catalyst at a temperature of
455oC in 1 hour reaction time. The oil separated from the first step was further treated in
the second step by 30% (v/v) methanol and 1% (v/v) H 2SO4 with 1 hour reaction time at
the same temperature. The treated oil was subjected to alkaline transesterification with 1:9
molar ratio of oil to methanol and 1.5 % (w/v) potassium hydroxide as the base catalyst at
a temperature of 503oC with 40 minutes reaction time. The result obtained shows better
biodiesel yield using lower acid catalyst concentration compared with the reference study.

Keywords: Rubber seed oil, transesterification, Biodiesel

1. Introduction

Energy security is the constant availability and supply of affordable energy for consumers and
industry. Risks to energy security include disruptions to the supply of imported fossil fuels, limited
availability of fuel, and energy price hikes. Many countries have already implemented deriving
biofuels from locally available sources and using them as alternatives to petroleum products. India
has started minor projects with future perspectives and expected to be the stepping stone for large
ventures. Currently the Indian rail budget announces use of biodiesel up to 5% of total diesel fuel
consumption [1].

Corresponding Author to: 09605440515, 9447568494

Email: joy.eldhose@rediffmail.com,jilsesebastian@gmail.com
Vegetable oils are promising alternatives to diesel since their properties are nearer to diesel. Being
edible oils used as food, non-edible oil sources (more than fifty are identified) are preferred for the
application. The high viscosity and volatility of oil are incompatible to use in diesel engines. The
commonly employed methods to reduce the viscosity of the vegetable oils are blending with diesel,
emulsification, pyrolysis, cracking and transesterification [2]. Among these transesterification is the
most common method for biodiesel production.

Transesterification (alcoholysis) is the chemical reaction between triglycerides and alcohol in the
presence of catalyst to produce mono-esters. The long and branched chain triglyceride molecules
are transformed to mono-esters and glycerine. Transesterification process consists of three
consecutive reversible reactions. First reaction is conversion of triglycerides to diglycerides,
followed by the conversion of diglycerides to monoglycerides. The glycerides are converted into
glycerol and yielding one ester molecule in each step [3]. In the present study, Rubber Seed Oil
(RSO) is used for the production of biodiesel. The present study compares the results with that from
the previous studies in chemical methods and in developing a procedure for biodiesel production
from High Free Fatty Acid (FFA) contained RSO.

2. Characteristics of Rubber seed oil

The rubber tree (Hevea brasiliensis), is the source of rubber seed which is a main plantation crop in
Kerala. The fruits of rubber tree mature between July and September. These are ellipsoidal capsules
with three carpels each containing seed which weighing 2-4 grams and 2.5-3 cm long. The kernels
are separated by breaking the capsules. These kernels are dried to remove the moisture. The kernels
are crushed in the crushers and the oil is filtered. Commercially available oil will be in dark brown
color [4].

Table 1.Properties of rubber seed oil

Property Rubber seed oil
Fatty acid composition (%)
1. Palmitic acid C16:0 10.2
2. Stearic acid C18:0 8.7
3. Oleic acid C18:1 24.6
4. Linolic acid C18:2 39.6
5. Linolenic acid C18:3 16.3
Specific gravity 0.91
Viscosity (mm2/s) at 40oC 38.46
Flash point(oC) 210
Acid value (mgKOH/g) 82

The fatty acid composition of rubber seed oil consists of 18.9% saturation comprising of palmitic
and stearic acids and 80.5% unsaturation comprising mainly of oleic, linoleic and linolenic acids
(refer Table 1). Saturated fatty acid methyl esters increase the cloud point, cetane number and
improve stability whereas more poly-unsaturation reduces the cloud point and cetane number and
stability [3]. The type and percentage of fatty acids contained in oil depends on the plant species
and the growth conditions. The acid value of locally available rubber seed oil is found as 82% (free
fatty acid of 41%) by standard titration [AOCS] method [5].
3. Materials and Methodology

Rubber seed oil was collected from Pavalam & Co. Virudhunagar, Tamilnadu, one of the main
rubber seed oil production centers in South India. Methanol (99.8% pure), potassium hydroxide
(KOH) and sulphuric acid (H2SO4) purchased from Merck were used in analytical reagent grade. A
small scale laboratory reactor consisting of 1000 ml round flask and magnetic stirrer with hot plate
were the main components in the apparatus. The stirring speed was same for all processes.
Temperature measurements were done by mercury column thermometer.

3.1. Acid esterification

The difficulty of direct alkaline esterification of high FFA oils was overcome by acid esterification
using a strong acid catalyst [2]. For effective alkaline esterification the acid value of the untreated
feed stock oil is expected to be below 3%. A two-step acid esterification technique has been used to
reduce the acid value to desirable range.

3.2. Alkaline transesterification

After removing impurities the treated oil having low FFA value was carried to alkaline
transesterification for methyl ester production. The titration method considered is laboratory level
AOCS standard titration. The oil collected was used directly without any treatment. A mixture of
50% iso-propanol and 50% toluene with 5g oil was titrated against 0.1N KOH solution using
phenolphthalein as the colour indicator.

After each acid esterification the reacted mixture was kept in a separating funnel through an
overnight for the separation. Methanol and water form a single layer settled at the top and residue
of cream white color at the bottom and the treated oil lie in between these two layers. The
hydrolysis activity produces water which inhibits the reaction during esterification [6]. For better
results, after each acid esterification step the reacted mixture was properly separated by giving
sufficient time to settle.

4. Acid Esterification (Two step retreatment process) of rubber seed oil

Ramadhas et al. [3] investigated acid esterification of rubber seed oil (FFA of 17%) with single step
reaction. Satyanarayana and Muraleedharan [4] employed a two-step pre-treatment of rubber seed
oil (FFA of 24%) with 0.75% v/v methanol to oil molar ratio with 1% H 2SO4 for 1h at 632oC.
Junaid Ahammed et al. [7] investigated with oil of 42%FFA content and found to be a molar ratio of
1:15 and 10% w/v of acid catalyst with 90 minutes of reaction time at 45oC as optimum conditions.

Five sets of experiments were conducted with varying oil to alcohol molar ratio and acid catalyst
concentration for the reduction of FFA content. In each run 200ml of rubber seed oil was filled in
the flask and preheated to 50oC. Determined amount of methanol was then added to the oil and
started stirring. After a few minutes acid catalyst was added to the mixture and continued stirring.
Different methanol to oil molar ratios of 0.20, 0.40, 0.50, 0.60, and 0.65 were done in the first step
with reaction time of 1h keeping reaction temperature of 455 oC throughout the reaction with acid
catalyst of 1% (v/v). The mixture then poured into the separating funnel and kept for separation.
Water and methanol mixture along with sulphuric acid content moved to top. There was a layer of
residue settled at the bottom containing coloring pigments, gum forming agents wax etc. The
second step was done with 0.20, 0.35, 0.30, 0.20, and 0.20 of methanol ratios respectively, keeping
the other parameters as same in the first step. The result obtained was showing a better condition of
80% v/v methanol to oil and 2% v/v of H 2SO4 with 2h reaction time keeping the temperature at
455oC as constant. Investigation was also carried out with varying acid catalyst concentration with
optimum alcohol to oil molar ratio for any significant reduction in FFA value. It was found that
there was no significant reduction of FFA value by increasing the acid catalyst concentration.

5. Alkaline transesterification of rubber seed oil

Alkaline transesterification was carried out after the above mentioned two step pretreatment. The
base catalyst used was KOH (85% assay) and molar ratio of oil to ethanol was always kept as 1:9 in
each experimental run. The base catalyst concentration varies from 0.5wt% to 2wt% and the yield
obtained was investigated. The result was showing an increase in FAME yield with increase in
catalyst concentration. A 150ml of treated oil preheated to 50oC and solution of KOH and methanol
of required quantity were properly mixed and added to the heated oil along with stirring. Maximum
yield of 90% was obtained with 45ml methanol and 2.04g KOH (1.5wt %) catalyst. The
temperature was maintained at 553oC throughout the experiment for 40 minutes reaction time.
After completing the reaction, products were allowed to settle throughout a night. Glycerin was
removed after settling at the bottom. The top layer was purified by washing 3-5 times with
demineralized water at room temperature.

6. Results and Discussion

6.1. Acid esterification of Rubber seed oil

The alcohol to oil molar ratio is an important parameter to determine the conversion efficiency and
acid value reduction. The alcohol used here is methanol, a low cost chemical but the amount of
alcohol used in both acid esterification and alkaline esterification plays a significant role in
production cost of biodiesel. Experiments started from 20%v/v methanol (refer Figs. 1 and 2) and a
better reduction in acid value was observed by increasing percentage of oil-alcohol ratio. But the
use of excess alcohol was not giving such a significant reduction of acid value. The residue and
methanol water mixture separated after the reaction was observed on bottom and top respectively at
20%, 40%, 60% and both are at the top in 50% and 65% molar ratios. The maximum conversion
efficiency was obtained at 1:12 molar ratio. The result obtained from pre-treatment process shows
comparatively less methanol ratio with Satyanarayana (FFA of 24% rubber seed oil uses 75%
methanol in two step pre-treatment). The reaction time in the investigation was 30 and 60 minutes,
and observed that the latter was sufficient for completing the reaction in each step of acid
esterification.

Reaction temperature was always maintained at 455 oC.The increase in temperature above 55 oC
was led the product to become dark in color and not suitable for further treatment. The untreated oil
carried all the adulterants at the time of oil extraction used for acid esterification. The mild
temperature condition observed will reduce the heat input for the reaction. Experiments were
conducted with varying acid catalyst amount from 1% to 4% with favorable methanol ratio.
Maximum conversion efficiency was obtained at 2 % (v/v) H2SO4. Junaid Ahammed et al. [7] did
experiments with 10wt% H2SO4 in which 45% FFA rubber seed oil was reduced to 0.82% in single
step acid treatment. A better acid value reduction (Fig. 3) of 4.06 (FFA of 2.03%) reached with total
2 % (v/v) acid catalyst in two step pre-treatment.
 Fig.1. Variation in FFA reduction with methanol ratio

Fig. 2. Treated oil conversion efficiency with various methanol ratios

(After first step pretreatment)
 Fig. 3. FFA variation with acid catalyst amount

6.2. Comparisons of acid esterification with previous studies

Comparison of variables (methanol ratio, acid catalyst amount, reaction time and reaction
temperature) in acid esterification reaction with literatures [4, 7] is given in Table 2. The results
shows a lower acid catalyst amount and lower methanol ratio as compared with the previous studies
in two step acid pretreatment of high acid value rubber seed oil. The results obtained from the
present study show the use of comparatively lower methanol ratio and significant reduction in acid
catalyst amount.

Table.2. Comparison of variables in acid esterification with existing literatures

Variable Satyanarayana and Junaid Ahammed Present study

Muraleedharan et al.
FFA value 24% 42% 41%
Treatment steps Two step Single step Two step
Methanol ratio 75% 50% 80%
Acid catalyst amount 1%v/v 10wt% 2%v/v
Reaction time 1h 1.5h 2h
Optimum acid value reduction < 2mgKOH/g 0.820mgKOH/g 2.03mgKOH/g
o o
Reaction temperature 632 C 45 C 455oC

6.3. Transesterification of Rubber seed oil

The experiment was conducted to check the base catalyst amount for maximum yield of biodiesel
along with temperature and reaction time. Biodiesel conversion is complicated if oil contains large
amount of FFA (>3% w/w) which will form soap with alkaline catalyst. The soap can inhibit the
separation of the biodiesel from the glycerin fraction [8]. Acid esterified oil of 2.03% was used in
the present study. The researchers [3, 4] found that the maximum yield was at 455 oC and 555oC,
respectively. In this study it was found that 553 oC is sufficient for completion of reaction,
maintaining the same temperature until the reaction completes. The lower temperature increases the
reaction time and higher temperature reduces the FAME yield. It has been observed that 40 minutes
reaction duration is sufficient for alkaline transesterification of rubber seed oil compared with the
previous studies. Results obtained from the reaction show that increase in reaction time did not give
such a comparable yield.
The strong base catalyst here used was KOH and it plays the major role in methyl ester production.
Thangaraj and Paul Raj [9] reported that biodiesel production with 1.45% NaOH gives a yield of
85% at 1h reaction time. Base catalyst concentration was varied from 0.5wt% to 2wt% in the
present study and the result revealed that maximum yield of 90% was obtained with a base catalyst
concentration of 1.5wt%. Emulsion was observed with lower catalyst concentrations (0.5 - 1wt%)
due to insufficient catalyst amount to completely neutralize the entire FFA resulting in
saponification reaction.

Fig. 4. Effect of ctalyst concentration on Conversion efficiency

The entire process which includes the two step acid treatments and alkaline transesterification can
be summarised as shown in Fig. 5 below.
 Rubber seed oil Acid value Acid Methanol,
estimation esterification H2SO4

Separation and acid

value estimation

Acid esterification Methanol

,H2SO4

Separation and acid

value estimation

Alkaline Methanol,
Transesterification KOH

Biodiesel

Fig. 5. Steps in biodiesel preparation from rubber seed oil

7. Conclusion

The acid value reduction of rubber seed oil with high FFA and methyl ester production are
investigated in this study. It is found that direct alkaline transesterification or acid esterification
could not be used for high FFA feed stocks. The reason is that FFA in oil has hydrogen radicals
which produce more complex polymer network and soap content. Effect of variables in acid
esterification and alkaline transesterification was studied and compared with previous studies. The
two stage acid esterification required to reduce FFA from 41% to 2.03% with low acid catalyst
amount was considered here. The alkaline catalyzed transesterification converts the product of first
step into its methyl ester and glycerin. The effect of alcohol to oil molar ratios, temperature, acid
catalyst amount and reaction time was analyzed in each step. A favorable molar ratio of 80% and
acid catalyst amount of 2% were observed with two step acid esterification. Maximum ester
conversion is achieved at 1.5wt% base catalyst. The flash point of biodiesel is measured as 168 oC
which is greater than that of diesel and calorific value, less than that of diesel.

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